Advances in Photochemistry by Noyes W

By Noyes W

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On the other hand, this still does not explain Wiseman's results, which if not an artifact due to anisotropy, definitely imply the operation of acceptor orbitals on the bridging sulfur atom. 28 M~CX:\P-R H / (I) R = dimethylamino exists as an equilibrium mixture of trans and cis isomers in 83: 17 ratio, respectively. R =isopropyl prefers the cis configuration. Conclusions References The downfield shift for H-2 upon anion formation proves that carbon-2 is trigonal, since acyclic sulfones show an upfield shift upon carbanion formation.

6% lower than those of (B-68c). This demonstrates the unreliability of force constants as a means of studying dp-rr bonding. (D-64) IR and Raman spectra of (CI3Si)20 could be interpreted by D3d or D3H structure with large Si-O-Si angle (but < 180°). Symm Si-O-Si str. 332 cm- 1, IR & Raman active, antisym Si-O-Si str. 1115 cm- 1, IR active only. Strong coupling of symmetric SiOSi and SiCI3 stretching vibrations, explaining low symm. SiOSi stretch. (DH-69) IR and Raman spectra show N[P(CF 3h 13 to be pyramidal with very weak P-N bonds, in agreement with the easy cleavage of the P- N bond by HCI or ammonia.

Perkins (P-67) showed that dP-1T bonding in trisilylamine, although favored by planarity, does not require it. Proton chemical shifts have been used to study dP-1T conjugation between sulfur and a carbon-carbon double bond. The chemical shifts of the (3-trans protons of phenyl vinyl ether and phenyl vinyl sulfide were at higher and lower field, respectively, than that in allylbenzene. Consequently, assuming anisotropy can be neglected in this system, the conjugation between sulfur and the olefinic electrons is dP-1T rather than PP-1T as with oxygen (KKF-73).

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